Reaction products of a polymer of a vinylene ester and a nitrogenous compound



United States Patent '0 REACTION PRODUCTS OF A POLYMER OF A VINYLENEESTER AND A NITROGENOUS COMPOUND Erhart K. Drechsel, Springdale, Conn,assignor to American Cyanamid Company, New York, N.Y., a corporation ofMaine No Drawing. Application May 13, 1954 Serial No. 429,689

18 Claims. (Cl. 260-72) This invention relates to the production of newsynthetic materials and, more particularly, new resinous (or potentiallyresinous) compositions which are especially suitable for use in theplastics and coating arts. My new compositions are obtained by reactionbetween ingredients comprising (1) a polymer (including bothhomopolymers and copolymers or interpolymers) of an unsaturated ester,more particularly an unsaturated carbonate, and specifically vinylenecarbonate containing at least mole percent of combined vinylenecarbonate) and (2) at least one nitrogenous compound selected from theclass consisting of ammonia, primary amines (including both the primarymonoamines and polyamines) and the secondary amines (including both thesecondary monoamines and polyamines). The scope of theinvention alsoincludes aldehyde-reaction products, specifically formaldehyde-reactionproducts, of the aforementioned reaction products of a polymer ofvinylene carbonate and the aforesaid nitrogenous compound, as well asmethod features. Instead of an aldehyde as a reactant, other activecarbonylcontaining compounds can be used, e.g., a ketone.

Illustrative examples of amines that can be used as a reactant with theaforementioned polymer of vinylene carbonate are the alkanol monoamines,e.g., the ethanol monoamines, propanol monoamines, etc., containing atleast one hydrogen atom attached to the amino nitrogen atom; thehydrocarbon-substituted monoamines containing at least one hydrogen atomattached to the amino nitrogen atom, e.g., the primary and secondary,saturated and unsaturated aliphatic,(including cycloaliphatic)hydrocarbon monoamines, the primary and secondary aromatic hydrocarbonmonoamines, the primary and secondary, aromatic-substituted aliphatichydrocarbon monoamines, and the aliphatic-substituted aromatichydrocarbon monoamines; the polyalkylene polyamines containing at leastone amine grouping having at least one hydrogen atom attached to theamino nitrogen atom; and others that will be apparent to those skilledin theart from the foregoing general examples and from the more specificexamples given hereinafter. Thus, it will be apparent that there alsocan be used amines containing one or more (e.g., two, three, four, fiveor higher number) primary amino groups together with one or more (e.g.,two, three, four, five or higher number) secondary amino groups, with orwithout hydroxyl or other active or inactive groups (e.g., tertiaryamino groups) attached to the chain. Hydrazine and substitutedhydrazines containing at least one hydrogen atom attached to an aminonitrogen atom also can be employed as the amine reactant with thepolymer of vinylene carbonate.

In my copending application Serial No. 400,107, filed December 23, 1953,now Patent No. 2,794,013, dated May 28, 1957, I have disclosedcompositions comprising a reaction product of ingredients comprisingvinylene carbonate (monomeric vinylene carbonate) and ammonia, or aprimary or secondary amine, or a mixture of such nitrogenous compounds.The claims of the aforesaid patent specify that the reactant with thevinylene ice 2 carbonate is at least one nitrogenous compound selectedfrom the class consisting of ammonia and primary amines, the latterhaving only single bonds between anyadjacent carbon atoms of anystraight-chain radical which is a component thereof. The presentinvention is separate and distinct from the invention disclosed andclaimed in the aforementioned patent, as it involves the use of apolymer of vinylene carbonate in preparing a different kindof syntheticmaterial.

It is a primary object of the present invention to prepare a new classof synthetic materials, more particularly resinous compositions, whichhave particular utility in the plastics and coating arts, e.g., ascoating, laminating, adhesive, impregnating, casting and moldingcompositions and other applications can be prepared by effecting re-:

action between ingredients comprising (1) a polymer of vinylenecarbonate containing at least 10 mole percent of combined vinylenecarbonate and up to mole percent of a different compound which iscopolymerizable with vinylene carbonate and which contains a CH '=Cgrouping, and (2) at least one nitrogenous compound selected from theclass consisting of (a) ammonia, ([2) primary amines and (c) secondaryamines. Mixtures of any two or all three of the nitrogenous compounds of(a), (b) and (c) in any proportions can be used, if desired. The polymerof vinylene carbonate may be homopolymeric vinylene carbonate or it maybe a copolymer containing at least 10 mole percent ofcombinedvinylenecarbonate, e.g., one containing from 10 or 15 to 90 or or even as highas 99.9 mole percent of combined -vinylene carbonate. Advantageously, ifa copolymer be employed, it is one which is a product of polymerizationof a mixture of copolymerizable ingredients including (a) vinylenecarbonate and (b) a different compound containing a CH =C grouping, moreparticularly a single CH =C grouping (e.g., vinyl chloride, vinylidenechloride, styrene, the various methyl-, ethyland' other loweralkyl-styrenes, the various chlorostyrenes, acrylonitrile,methacrylonitrile, acrylamide, methocrylamide, etc.), the vinylenecarbonate of (a) constituting at least 50 mole percent, moreparticularly from 60 to 95 mole percent, of the said mixture ofcopolymerizable ingredients.

Vinylene carbonate has the formula I 11?:011

C II 0 When ammonia or a primary saturated aliphatic mono amine isemployed as a reactant with a polymer of vinyl-i ene carbonate theinitial reaction which takes place may be illustrated by the followingequation, and for purpose The reaction product of Equation II is capable:of

undergoing inter-reaction between molecules thereoftto formhigher-molecular-weight polymers. Or, the reaction product of EquationII can be reacted with an active p 2,930,179, 1 Patented Mar. 29, 1960.

carbonyl-containing compound or compounds, for in- The N-carbinol,specifically N-methylol, derivative obtained by the above reaction iscapable of further reaction to form the corresponding N-methylenederivatives and cross-linked resinous polymers, that is, polymers in acured or substantially insoluble, substantially infusible state.

The choice of the active carbonyl-containing compound, which is used asa reactant with the reaction product of the polymer of vinylenecarbonate and the aforesaid nitrogenous compound, is dependent largelyupon economic considerations and the particular properties desired inthe finished product. I prefer to use as the active carbonyl-containingcompound an aldehyde, and more particularly formaldehyde or compoundengendering formaldehyde, e.g., paraformaldehyde,hexamethylenetetramine, trioxane, etc. Illustrative examples of otheraldehydes that may be employed are acetaldehyde, propionaldehyde,butyraldehyde, heptaldehyde, octaldehyde, acrolein, methacrolein,crotonaldehyde, benzaldehyde, furfural, hydroxyaldehydes (e.g., aldol,glucose, glycollic aldehyde, glyceraldehyde, etc.), mixtures thereof, ormixtures of formaldehyde (or compounds engendering formaldehyde) withsuch aldehydes. Illustrative examples of aldehyde-addition products thatmay be used instead of the aldehydes themselves are the monoandpoly-(N-carbinol) derivatives, more particularly the monoandpolymethylol derivatives, of urea, thiourea, iminourea, and ofsubstituted ureas, thioureas and iminoureas, monoand poly-(N-carbinol)derivatives of amides of polycarboxylic acids, e.g., maleic, itaconic,fumaric, malonic, succinic, citric, phthalic, etc., monoandpoly-(N-carbinol) derivatives of the aminotriazines, of theaminotriazoles, of the aminodiazines, etc. Good results are obtainedwith aldehyde-addition products such as methylol urea and thiourea,especially monoand dimethylol ureas and thioureas, and a methylol mel-'amine, e.g., monomethylol melamine and polymethylol melamines (di-,tri-, tetra-, pentaand hexamethylol melamines). Mixtures of aldehydesand aldehyde-addition products may be employed, e.g., mixtures offormaldehyde and methylol compounds such, for instance, as dimethylolurea, trimethylol melamine, hexamethylol melamine, etc.

Illustrative examples of ketones that may constitute the activecarbonyl-containing compound are acetone, methyl ethyl ketone, methylpropyl ketone, cyclobutyi ketone, benzophenone, 2-propanone,2,4-pentanedione. 2- pentanone, 3-pentanone, 4-heptanone, acetophenone,propiolphenone, etc.

Instead of using a single aldehyde or a single ketone as the activecarbonyl-containing compound, I may use a plurality of differentaldehydes, or a plurality of different ketones, or a mixture of analdehyde and a ketone in any proportions.

In addition to ammonia and the monoamines, a polymer of vinylenecarbonate containing at least mole percent of combined vinylenecarbonate also is reactable: with polyamines containing at least onehydrogen atom attached to an amino nitrogen atom. The reaction of 4 theaforementioned vinylene carbonate polymers with such polyamines may beillustrated by the following equation where a polyamine represented bythe formula H NRNH where R represents an alkylene radical, is taken asillustrative of the amine reactant:

In preparing the reaction product (vinylene carbamate polymer) of thevinylene carbonate polymer with the aforementioned nitrogenous compound(that is, ammonia or a primary or secondary amine) the proportions ofthe reactants can be widely varied depending, for example, upon theparticular starting reactants employed and the particular conditions ofreaction. The amount of the nitrogenous compound should be sufi'icientto react with at least one of the vinylene carbonate units in thepolymer molecule, more particularly from one to all of the aforesaidvinylene carbonate units. Ordinarily the nitrogenous compound isemployed in an amount such that at least 1%, preferably at least 5%e.g., from 10 or 15% up to of the vinylene carbonate units are convertedinto the corresponding carbamate units.

The temperature of the reaction also can be varied considerablydepending, for instance, upon the particular reactants employed, therapidity of the reaction wanted, the particular properties desired inthe reaction product, and other influencing factors. For example, thereaction temperature can be varied from room temperature (20 30 C.) upto about 100 C., preferably not higher than about 60 or 65 C. if thereaction can be caused to proceed at the lower temperatures. Thereaction mass is cooled, if necessary, in order to keep the temperaturethereof to the optimum temperature of reaction.

The reaction can be effected in the absence of a solvent or otheradditive, or in the presence of (i.e., intimately associated with) arelatively inert solvent (e.g., water, benzene, toluene, xylene,dioxane, acetone, ethyl methyl ketone, methyl isobutyl ketone,chlorobenzene, chloroform, ethylene dichloride, methanol, ethanol,propane],

butanol, pentanol, hexanol, allyl alcohol, methallyl alcohol, benzylalcohol and other monohydric alcohols, including those belonging to thesaturated and unsaturated aliphatic and aromatic-substituted aliphaticseries; the various liquid alcohol-others, for example, ethylene glycolmonomethyl ether, ethylene glycol monoethyl ether, diethylene glycolmonomethyl ether, diethylene glycol monoethyl ether, etc.; as well asnumerous others that will be apparent to those skilled in the art. Anexcess of the amine reactant over stoichiometrical proportions mayconstitute the medium in which the reaction is effected. The inert oractive liquid medium or additive, if employed, can be used in anysuitable amount ranging, for instance, from 0.1 to 40 or 50 times thatof the weight of the primary reactants (polymer of vinylene carbonateand ammonia or a primary or secondary amine in reactive proportions).Good results are obtained when the liquid reaction medium is employed inan amount such that the primary reactants constitute from about 20% toabout 30 or 35% by Weight of the reaction mass. At the end of thereaction period, the inert or unreacted liquid medium is then removedfrom the reaction mass by any mom . suitable means, for example bydistillation, decantation, etc., or the solid reaction product can beseparated from the liquid component of the reaction mass by filtration,centrifuging, etc.

For certain applications it may be desirable to modify the properties ofthe carbamate polymers of this invention. One method of effecting thisresult is to react this polymer with an active carbonyl-containingcompound, especially an aldehyde, e.g., formaldehyde. For this purposethe ratio of the aldehydic reactant to the carbamate polymer may bevaried as desired or as conditions may require, the proportionsdepending upon such influencing factors as, for instance, the particularcarbamate polymer and aldehydic reactant employed and the particularproperties desired in the finished product. If the aldehydic reactant isan aldehyde, e.g., formaldehyde, it is used in an amount sufficient toreact with at least one of the reactive amino groups in the polymer,more particularly from one to all of the aforesaid'reactive aminogroups. Ordinarily the aldehydic reactant is employed in an amount suchthat at least 1% of the hydrogen atoms attached to the amino nitrogenatom of the carbamate polymer are replaced either by alkylol(specifically methylol) groups or by dehydration products thereof. ThusI may use, for example, from 0.5 to 2 moles of the aldehyde for eachaldehyde-reactable recurring vinylene carbamate unit in the polymer.

When the aldehyde is available for reaction in the form of an alkylolderivative, more particularly a methylol derivative, e.g., dimethylolurea, trimethylol melamine, etc., amounts of such alkylol derivativescorresponding to or higher (e.g., from a few percent more to or times asmuch) than the relative amounts mentioned above with reference to thealdehyde may be used. When the aldehydic reactant is a reactive productof reaction of ingredients comprising an aldehyde and, for example, anamidogen compound that has been reacted beyond the alkylol stage, but isstill capable of co-reacting with the carbamate polymer, then theproportions thereof with respect to the said polymer may be either moreor less than those proportions just mentioned with respect to the use ofan aldehyde or an alkylol derivative as the aldehydic reactant.Depending upon the particular starting reactants employed and theparticular properties desired in the finished product, the weightproportions of reactants'(i.e., aldehydic reactant and carbamatepolymer) can range, as desired or as conditions may require, from 1:99to 99:1, more particularly from 10:90 to 90:10, bearing in mind thatwhen the aldehydic reactant is an ordinary aldehyde the proportions areusually of the order of those given in the preceding paragraph.

The reaction between the aldehydic reactant and the polymer of thevinylene carbamate can be efiected under a wide range of pH conditions(i.e., acid, alkaline or neutral conditions, for example a pH offrom-about 1 or 2 to about 11, and more specifically a pH of from about6 to about 9).

Any suitable temperature can be employed for effecting reaction betweenthe carbamate polymer and the aldehydic reactant. In some cases thereaction can be initiated at room temperature (20-30 C.). Ordinarily,the temperature of the reaction varies between about 60 C. and thereflux temperature of the reaction mass when the reaction is carried outat atmospheric pressure in the presence of a solvent or diluent. If thereaction be carried out at pressures above atmospheric, temperatures ashigh as, for example, 200-22S C. or even higher may be employed.

The reaction between the aldehydic reactant, e.g., formaldehyde, abutylated melamine-formaldehyde partial reaction product, a methylol(cg, monomethylol or dimethylol) methacryloguanamine, dimethylol urea,tri-' methylol melamine, etc., and the carbamate polymer can be carriedout in the presence of solvents or diluents, other natural or syntheticbodies (numerous examples of which hereafter are given), or whileadmixed with 'other materials which are reactable or non-rca'ctablewiththe aldehydic reactant or with the aforementioned polymer,

e.g., urea, thiourea, cyanamide, dicyandiarnide, phthalic diamide,acetamide, chlorinated acetamides, methyl ethyl ketone, etc.;aldehyde-reactable triazines, e.g., melamine, ammeline, ammelide, etc.;phenol and substituted phenols, e.g., the cresols, the xylenols, thetertiary-alkyl phenols, etc.; monohydric and polyhydric alcohols, e.g.,butyl alcohol, amyl alcohol, heptyl alcohol, n-octyl alcohol,2-ethylhexyl alcohol, ethylene glycol, propylene glycol, glycerine,polyvinyl alcohol, etc.; amines, including aromatic and aliphaticamines, e.g., aniline, tributylamine, diamylam-' ine, etc.; and thelike.

If the reaction between the carbamate polymer and the aldehydic reactantis carried out'in the presence of ammonia or a primary or secondaryamine, then one can effect simultaneous reaction between the aldehydeand the amino groups of the carbamate units of the polymer on the onehand, and between the ammonia (or primary or secondary amine, if used)and any vinylene carbonate units in the polymer that were not'previouslyconverted into carbamate units on the otherhand. Such newly createdcarbamate units of the polymer then can react with aldehydic reactant ashereinbefore described.

The modifying reactants may be incorporated with the carbamate polymerand the aldehydic reactant to form an inter-reaction product by mixingall the reactants 'and effecting reaction therebetween under acid,alkaline or neutral conditions or by various permutations of reactants.For example, I may effect partial reaction or,

more particularly, condensation between the chosen aldehydic reactantand the polymer, then add the modifying reactant, e.g., urea, melamine,etc., and effect further reaction. Or, I may first partially react urea,melamine or other aldehyde-reactable mcdfying reactant with a molecularexcess of an aldehyde under acid, alkaline or neutral conditions, thenadd the carbamate polymer and effect further reaction. Or, I mayseparately'partially react 1) urea, melamine or other aldehyde-reactablemodifying reactant and an aldehyde and (2) a'carbamate polymer of thekind used in practicing one embodiment of the present invention and analdehyde, thereafter mixing the two products of partial reaction andeffecting further reaction therebetween. The reactants of 1) and (2)initially may be partially reacted under acid, alkaline or neutralconditions. 7

It will be understood, of course, by those skilled in the art thatreference hereinbefore and later herein to aldehyde or aldehydicreactant" in describing the process, reaction conditions, etc., has beenfor ease of description, that it is not intended to be limiting innature, and that, instead of an aldehyde, an equivalent amount of aketone or other active carbonyl-containing compound can be used. Asmentioned'hereinbefore the polymer of. the

combined vinylene carbonate. From a cost and efficiency standpoint it isalso desirable that the monomer which, is copolymerized with thevinylene carbonate be one which is free from groups that, duringreaction between the copolymer and the ammonia, or primary or secondaryamine, might be reactive with the latter or might hy-,

drolyze under the reaction conditions.

The polymer (homopolymer or copolymer); of vinylene carbonate employedcan be of any desired moleculanri". weight, for example an averagemolecular 'weightranging between about 500 and about 5,000,000 or moreas de termined by viscosity measurementsusing the Staudinger, equation.

The substance which is copolymerized with i .7 carbonate to form thecopolymer can be a compound which is difierent therefrom, which iscopolymerizable therewith and which contains a polymerizable ethyleniclinkage, more particularly a CH =C grouping.

Examples of such substances that can be copolymerized with vinylenecarbonate in the proportions hereinbeiore mentioned, singly or aplurality (two, three, four or any desired number) thereof, the latteroften being desirable in order to improve the compatibility andcopolymerization characteristics of the mixture of monomers and toobtain a copolymer intermediate having theparticular properties desiredfor a particular use thereof are such monomers as the unsaturatedalcohol esters, more particularly the allyl, methallyl, crotyl,l-chloroallyl, 2-chloroallyl, cinnamyl, vinyl, methvinyl, l-phenylallyl,butenyl, etc., esters of saturated and unsaturated, aliphatic andaromatic, monobasic and polybasic acids such, for instance, as acetic,propionic, butyric, valeric, caproic, acrylic and alpha-substitutedacrylic (including alkacrylic, e.g., methacrylic, ethacrylic,propacrylic, etc., and aryacrylic, e.g., phenylacrylic, etc.), crotonic,oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic,sebacic, fumaric, citraconic, mesaconic, itaonic, acetylenedicarboxylic, aconitic, benzoic, phenylacetic, phthalic, terephthalic,benzoylphthalic, etc., acids; the saturated monohydric alcohol esters,e.g., the methyl, ethyl, propyl, isopropyl, butyl, sec.butyl, amyl,etc., esters of unsaturated aliphatic monobasic and polybasic acids,illustrative examples of which appear above; vinyl cyclic compounds(including monovinyl aromatic hydrocarbons), e.g., styrene, mandp-chlorostyrenes, -bromostyrenes, -fluorostyrenes, -methylstyrenes,-ethylstyrenes, -cyanostyrenes, the various polysubstituted styrenessuch, for example, as the various di-, triand tetrachlorostyrenes,-bromostyrenes, -fluorostyrenes, -methylstyrenes, -ethylstyrenes,-cyanostyrenes, etc., vinylnaphthalenes, vinylcyclohexanes,viuylfuranes, vinylpyridines, divinylbenzenes, trivinylbenzenes,allylbenzenes, diallylbenzenes, N-vinylcarbazole, the various allylcyanostyrenes, etc.; the various alpha-substituted styrenes andalpha-substituted ring-substituted styrenes, e.g., alpha-methylstyrene,alpha-methyl-para-methyl styrene, etc.; unsaturated ethers, e.g., ethylvinyl ether, diallyl ether, ethyl methallyl ether, etc.; unsaturatedamides, for instance N-allylcaprolactarn, acrylamide and N-substitutedacrylamides, etc.; unsaturated ketones, e.g., methyl vinyl ketone,methyl allyl ketone, etc.; methylene malonic esters, e.g., methylenemethyl malonate, etc.; unsaturated aliphatic hydrocarbons, e.g.,ethylene, propylene, butadienes, e.g., 1,3-butadiene, 2-chlorobutadiene,etc.; unsaturated polyhydric alcohol (e.g., butenediol, etc.) esters ofsaturated and unsaturated, aliphatic and aromatic, monobasic andpolybasic acids, illustrative examples of which appear above;unsaturated glycidyl esters such as glycidyl acrylate, glycidylmethacrylate, glycidyl itacouate, glycidyl allyl phthalate, etc.

Other examples of monomers that can he c0polymerized with vinylenecarbonate, and which constitute a preferred class in making vinylenecarbonate copolymers for use in practicing the present invention, arethe vinyl halides, more particularly vinyl fluoride, vinyl chloride,vinyl bromide and vinyl iodide, and the various vinylidene compounds,including the vinylidene iodide, e.g., vinylidene chloride, vinylidenefluoride and vinylidene iodide, other comonomers being added if neededin order to improve the compatability and copolyrnerizationcharacteristics of the mixed monomers.

Other and more specific examples of monomeric materials which can bemixed or blended with vinylene carbonate in the aforementionedproportions, and the resulting homogeneous or substantially homogeneous,poiymerizable composition then polymerized to yield copolymerintermediates for use in practicing the present invention are the allylcompounds and especially those which have a boiling point of at leastabout 60 C. Of

the monomeric materials which can be used the allyl esters form alargeclass. The reactive allyl compounds employed are preferably those whichhave a high boiling point such, for example, as diallyl maleate, diallylfumarate, diallyl phtbalate, diallyl succinate, etc. Other allylcompounds which are not necessarily high boiling also may be used.

Additional examples of allyl compounds, and of other compoundscontaining one or more CH ==C groupings that can he used in producingthe copolymer intermediates empioyed in carrying one embodiment of myinvention into effect are given in, for example, Drechsel and PadburyPatent No. 2,550,652, dated April 24, 1951, and especially in thatportion thereof with particular reference to monomers used in formingcoopolymers with diallyl cyanamide alone or with other comonomers. Stillother examples of cornonomers that can be polymerized with vinylenecarbonate, individually or a plurality thereof, are given in thecopending application of John A. Price and John I. Padbury, Serial No.353,666, filed May 7, 1953, now Patent No. 2,722,525, dated November 1,1955.

Other examples of copolymerizable substances that can be copolymerizedwith vinylene carbonate to form the copolymer intermediate include thepolymerizable unsaturated alkyd resins (modified or unmodified), e.g.,ethylene glycol maleate, diethylene glycol maleate phthalate, ethyleneglycol maleate succinate and dietha ylene glycol maleate linoleate. Aswill be understood by those skilled in the art, the unsaturated alkydresin and vinylene ester are chosen from those which are compatible andcopolymerizable with each other. Other and more specific examples ofunsaturated alkyd resins that can be used are given, for example, inNyquist and Kropa Patent No. 2,503,209, dated April 4, 1950, and patentsreferred to therein (see, for instance, column 8, lines l-64). Theunsaturated alkyd resins contain a plurality of polymerizably reactivealpha, beta-enal groups,

and are prepared in accordance with technique well known to thoseskilled in the resin art.

Other examples of compounds that can be copolymerized with vinylenecarbonate to form the copolymer intermediate are given in Kropa PatentNo. 2,510,503 (e.g., column 2, line 46, to the end of the sentence inline 16, column 3; column 5, line 54, through line 46, column 7; andcolumn 13, line 42, through line 30, column 16; and in the aforesaidNyquist et al. Patent No. 2,503,209 (see, for instance column 5, line67, through line 75, column 7; and column 9, line 74, through line 12,column 11).

Mixtures of different compounds containing a CH C grouping, or mixturesof different unsaturated alkyd resins, or mixtures of a compoundcontaining a CH C grouping and an unsaturated alkyd resin can be used asthe unsaturated material in forming the copolymer intermediate.

The vinylene carbonate homopolymers and copolymers used in practicingthe present invention can be produced by any suitable means, forinstance as described in the aforementioned Price and Padbury copendingapplication Serial No. 353,666 with particular reference to theproduction of vinylene carbonate copolymers; also, as described in theaforementioned patents with reference to the preparation of othercopolymers. In other words, the vinylene carbonate homopolymers andcopolymers are prepared by conventional methods used in producing otherhomopoly ners and copolymers.

In order that those skilled in the art may better understand how 1epresent invention can be carried into effect, the following examples aregiven by way of illustration and not by way of limitation. All parts andpercentages are by weight.

The above ingredients are mixed together in a suitable reaction vesselprovided with a reflux Condenser and heated therein to reflux, and thenmaintained at the reflux temperature of the mass (about 142 C.) for 3hours. The reaction mass containing homopolymeric vinylene carbonate insolution is permitted to cool. After filtering off a trace of solidparticles that are present, the amber-colored polymer solution is usedin a series of additional reactions herinafter described.

To 350 parts of the aforementioned cumene solution containing oneequivalent of homopolymeric vinylene carbonate is added 58 parts ofapproximately 29% aqueous ammonia (17 parts NH or 1 mole) and 200 partsof water. This is vigorously stirred for 2 hours at room temperature(20-30 C.). A mild exothermic reaction takes place. The aqueous layercontaining the ammonia reaction product (vinylene carbamate polymer)settles readily without emulsion formation and is readily separated fromthe organic phase. The cumene phase can be Washed, if desired, withadditional water to recover any vinylene carbamate polymer retainedtherein, and the washings then combined with the main aqueous portion.

Evaporation of a portion of the aqueous vinylene carbamate polymersolution cast on glass, in a 105 C. oven, yields a hard film. Whenanother portion is applied to cotton fabric, followed by drying in anoven at 105- 110 C. for about 16 hours, reaction with the celluloseapparently takes place as evidenced by the fact that about 20% of thevinylene carbamate polymer is retained after continuous aqueousextraction of the treated cloth to a constant weight.

Example 2 This example illustrates the preparation of analdehyde-reaction product, specifically a formaldehyde-reaction product,of the vinylene carbamate polymer of Example 1.

Example 1 is repeated. After separation of the aqueous phase theremaining cumene solution is washed first with 81 parts of an aqueoussolution of formaldehyde containing approximately 37% HCHO and 150 partsof water. The resulting aqueous phase is then combined with thepreviously separated aqueous solution containing most of the vinylenecarbamate polymer. The cumene solution is given a second wash with 90parts of water, and this washing also is added to the aforementionedaqueous solution of vinylene carbamate polymer. The aqueous solution isheated at 70 C. for about 30 minutes at a pH of about 7-8 to form theN-methylol derivative of homopolymeric vinylene carbamate.

A hard film is obtained when a portion of the aforementioned solution ofthe N-methylol derivative is cast on a plate of "glass and then heatedin a 105 C. oven for 1 hour. Treatment of cotton fabric with thesolution, as described in the preceding example, results in a somewhathigher retention of impregnant than that obtained with the vinylenecarbamate polymer of Example 1.

Example 3 an insoluble polymeric reaction product of the ethylenediamine and the homopolymeric vinylene carbamate is precipitated.

Similar results are obtained when any other primary or secondary pol'amine is substituted for the ethylene diamine of this example,,finstance diethylene triamine and tetraethylene pentamine.

Example 4 Example 1 is repeated with the exception that, instead ofpreparing and using homopolymeric vinylene carbonate as described inthat example, there is prepared and used a copolymer of acrylonitrileand vinylene carbonate. The method of preparing the copolymer is asfollows:

A reaction vessel equipped with a stirrer, reflux condenser, thermometerand gas-inlet tube, is placed in a constant-temperature bath which ismaintained at 35 C.

To the vessel is added a solution of 42 parts of acrylonie trile, 8parts of vinylene carbonate, 800 parts of water, and 0.05 part ofsulfuric acid. This is in a ratio of about 89.5 molar percent ofacylonitrile to about 10.5 molar percent of vinylene carbonate. The pHof the initial solution is 3. A rapid stream of pre-purified nitrogen ispassed over the surface of the solution for 30 minutes. The nitrogenflow is then reduced to about two or three bubbles per second. Areduction oxidation catalyst system (Redox system) is prepared bydissolving 1.71 parts of ammonium persulfate and 0.71 part of sodiummetabisulfite, each in parts water. The catalyst solutions are addedportion-wise to the reaction vessel at .forms is collected on a Biichnerfunnel, washed with 1000 parts of water and dried in an oven at 70 C.for 3 hours. Forty-five (45) parts of a dry, white copolymer ofacrylonitrile and vinylene carbonte is obtained.

To 350 parts of dimethyl formamide is added the aboveacrylonitrile-vinylene carbonate copolymer in an amount sufficient toform a solution containing one equivalent of the said copolymer. To theresulting solution is then added 58 parts of approximately 29% aqueousammonia (17 parts NH or 1 mole) and '200 parts of water. This isvigorously stirred for 2 hours at room temperature, yielding anammonia-reaction product of the coploymer, more particularly a vinylenecarbamateacrylonitrile copolymer in aqueous dimethyl formamide solution.Evaporation of a portion of the vinylene carbamate-acrylonitrilecopolymer solution cast on glass, in a C. oven, yields a hard film whichis more hydrophobic than the corresponding film made from the product ofExample 1.

The vinylene carbamate copolymer of this example can be reacted with analdehyde, specifically formaldehyde, as described in Example 2; and alsocan be crosslinked by reaction with a polyamine as described in Example3.

Example 5 A copolymer of vinylene carbonate and ethyl acrylate isprepared as follows:

are heated together under reflux at the boiling temperature of the massfor 5 hours. A viscous solution con raining a copolymer of ethylacrylate and vinylene car- I I bonate is obtained.

To the above vinylene carbonate-ethyl acrylate polymer solution inbenzene is added 3.66 parts of n-butyl 1 amine, and the resultingsolution is stirredat-room temperature for 2 hours to insurecompleteness of the reaction. The reaction proceeds exothermicallyalmost as soon as the reactants are brought into contact with eachother.

Cellulosic materials, e.g., cotton cloth and other cellulosic textiles,paper and paper products, etc., when treated with the resulting solutionof the n-butyl amine-reaction product (vinylene carbarnate-ethylacrylate copolymer) are thereby rendered more amenable to dyeing andprinting.

If desired, formaldehyde or other aldehyde-reaction products of thevinylene carbamate-ethyl acryliate copolymer can be made as hereinbeforedescribed.

Instead of ethyl acrylate other comonomers, more particularly otheresters of acrylic acid, e.g., methyl acrylate, propyl acrylate,isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, see-butylacrylate, tert.-butyl acrylate, amyl acylate, hexyl acrylate, propenylacrylate, cyclohexyl acrylate, phenyl acrylateQbenzyl acrylate, etc.,can be substituted in the above formulation to obtain a suitablecopolyrner intermediate. As with ethyl acrylate, so too with such othercomonorners the proportions of components can be widely varied withinthe range of from about to 99.9 ,rnolar percent of the vinylenecarbonate to from 90 to 0.1 molar percent of the other comonomer orcomonomers.

Example 6 Approx. Parts Molar Percent Vinyl acetate 50 50 Vinylenecarbonate... 50 50 Benzoyl peroxide 1 are mixed together and charged toa heavy-walled glass tube, which thereafter is sealed under vacuum.Copolymerization is eifected by heating the sealed tube in a 60 C. waterbath for 24 hours.

The hard copolymer thereby obtained is dissolved in 300 parts ofdioxane, and to the resulting solution is added 10 parts of piperidine.This solution is stirred for 4 hours at room temperature to insurecompleteness of the reaction.

Removal of the solvent by distillation or evaporation yields thepiperidine-reaction product (vinylene carbamate-vinyl acetate copolymer)which is more hydrophilic in its properties than the starting vinylenecarbonate copolymer intermediate. The dioxane solution of thepiperidine-reaction product can be diluted with water, if desired,without precipitating the said reaction product from solution.

The vinylene carbamate copolymer of this example is useful in theproduction of cast films, protective coating compositions, adhesives,laminating compositions, for textile and paper treatment and fornumerous other purposes. It is also amenable to reaction with formaldehyde and other aldehydes, as hereinbefore described, in order to obtainmodified products having improved properties for a particular serviceapplication.

Example 7 The following ingredients are charged to a polymerizationbottle:

The butadiene is the last component added. Sixty-one and four-tenths(61.4) parts of butadiene is added, the two parts excess being allowedto vaporize off, after which the bottle is scaled from the atmosphere.The bottle is placed in a constant temperature bath maintained at 30 C.and tumbled end over end for 39 hours. The bottle is opened, and thecopolymer of butadiene, acrylonitrile and vinylene carbonate isprecipitated from the resulting latex by adding thereto an aqueous 5%sodium cflrloride solution containing 2% sulfuric acid. The precipitatedcopolymer, more particularly a ternary polymer or tripolymer, isisolated, washed free of soluble contaminants and dried in a vacuumoven.

While kneading the tripolymer in a Banbury mixer, 10 parts ofdimethylaminopropylamine is added. After a period of 2 hours kneadingand reaction in the Banbury, a titration indicates the disappearance of50% of the aforesaid amine, which represents complete reaction to form acationic ternary polymer, which may be repre' sented as shown below:

I OH] I?'(GHz)a-N Example 8 Approx. Parts Molar Percent vinylenecaroonate 86 50 Vinyl butyl ether. 98 60 Benzene 200 Benzoyl peroxide 2are heated together under reflux at the boiling temperature of the massfor 5 hours. A viscous benzene solution containing a copolymer ofvinylene carbonate and vinyl butyl ether is obtained.

To 380 parts of the aforementioned benzene solution containing oneequivalent of vinylene carbonate copolymer is added 58 parts ofapproximately 29% aqueous ammonia (17 parts NH or 1 mole) and 200 partsof water. The resulting solution is stirred vigorously for 2 hours atroom temperature, the remainder of the procedure, testing and uses ofthe vinylene carbamate copolymer being the same as those described underExample 1 with reference to the preparation of homopolymeric vinylenecarbonate and subsequent treatment thereof.

Example 9 Approx. Molar Percent Vinylene carbonate Ketene dimethylaeetal.- Benzene Benzoyl peroxide Example 10 Example 1 is repeated. Tothe aqueous solution containing the homopolymeric vinylene carbamate andwater washings of the cumene solution combined therewith is added 50parts (slight excess) of cold acetaldehyde, and the mixture is stirredfor 10 hours while keeping the temperature at10 C., after which thereaction mass'is heated to 50 C. to remove the unreacted acetaldehyde.

The acetaldehyde-reaction product of the vinylene carbamate homopolymeris useful in such applications as mentioned in the preceding exampleswith reference to other products, and also as a modifier of naturalresins and other synthetic materials, especially synthetic resins. Itwill be understood, of course, by those skilled in the art that myinvention is not limited to the specific reactants, proportions thereofand conditions of reaction given by way of illustration in the foregoingexamples. For instance, instead of carrying out the reaction in thepresence of water or methanol, as in certain of the examples, thereaction can be efiected while the polymer of vinylene carbonate andamine reactant (ammonia, or a primary or secondary amine) are dissolvedor dispersed in various other liquid media, numerous examples of whichhave been given. hereinbefore. Likewise, aldehydes (or other activecarbonyl-containing compounds) other than the aldehydes employed inindividual examples can be used. Numerous examples of such activecarbonyl-containing compounds have been given hereinbefore. Also,instead of the particular amine reactant or mixture of amine reactantsset forth in the individual examples, the reaction with the polymer ofvinylene carbonate will proceed, to the best of my knowledge and belief,with any other primary or secondary amine, or with mixtures thereof inany proportion, or with any amines containing one or more primary aminogroups and, also, one or more secondary amino groups, with or withoutadditional tertiary amino groups. Thus, the amine reactant can be,

for example, ammonia or other nitrogenous compound having at least oneradical represented by the formula VI R where R represents hydrogen andR represents hydrogen or any monovalent organic (carbon-containing)radical, e.g., a hydrocarbon radical, a hydroxyhydrocarbon radical(e.g., hydroxyethyl, hydroxyphenyl, hydroxyxylyl, etc.), a heterocyclicradical (e.g., furyl, furfuryl, etc.), the radical -NH-NH and highermembers of the homologous series, etc. Other illustrative examples ofhydrocarbon and hydroxyhydrocarbon radicals which R in Formula VI canrepresent are given, for instance, in

Patent No. 2,582,594 dated January 15, 1952, column 2,' lines 20-54.Additional examples of sub-classes and of 14 Methyl amine(monomethylamine) Dimethyl amine Ethyl amine Propyl amine Dipropyl amineN-ethylbutyl amine (C H NHC H Dibutyl amine 2-amino-4-methylpentane [CHCHNH CH CH(CH l n-Amyl amine Di-n-amyl amine Hexyl amine Dihexyl amineHeptyl amine Diheptyl amine Octyl amine Dioctyl amine Decyl amineDidecyl amine Octadecyl amine Dioctadecyl amine 1,3-diaminopropaneS-diethylaminopropyl amine 1,3-diaminobutane (NH CH CH CHNH CH V1,3-bis-ethylaminobutane [C H NHCH CH CHNH C H CH 1,4-diaminobutane1,5-diaminopentane 1,6-diaminohexane 1,7-diaminoheptane1,8-diarninooctane Triethylene tetrarnine V [NH (CH CH NH CH CH NHTetraethylene pentamine Pentaethylene hexamine Propylenediamine(1,2-diaminopropane) Diethanolamine Hydroxyethyl ethylene diamineMonoisopropanolamine Diisopropanolamine Bis(3-aminopropyl) ether (NH CHCH CH O CH CH CH NH Bis(4-aminobutyl) ether Bis(5-aminoamyl) etherBis(6-aminohexyl) ether 0-, mand p-Phenylenediamines Benzidine2-aminobenzidine Aminoguanidine Guam'dine Monophenyl biguanide Hydrazine1,1-dimethylhydrazine Semicarbazide N-butylaniline m and p-Toluidineso-, mand p-Tolylenediamines p,p'-Diaminodiphenyl ether1,4-diaminoanthraquinone p,p'-Diaminodiphenylmethane 4-amino-2-butanoll-methylamino-Z-propanol (CH NHCH CHOHCH 5-isopropy1amino-1-pentanoll:HOCHZCH2CH2CH2CH2NHCH(CH3)2] Ethyleneimine Propyleneimine MorpholineThiamorpholine 2-methylmorpholine 3-ethylmorpholine3,5-dimethylmorpholine 2,3,5-trimethylmorpholine Furfuryl amine Asindicated hereinbefore, the properties of the fundamental resinuos ornon-resinous reaction products of this invention can be varied widely byintroducing other modifying bodies before, during or after effectingreaction between the primary components. Thus, as modifying agents I mayuse, for instance, urea and substituted ureas, aminotriazines (e.g.,melamine, ammelide, ammeline, etc.), monohydric alcohols, e.g., methyl,ethyl, propyl, isopropyl, butyl, hexyl, n-octyl, Z-ethylhexyl, decyl,dodecyl, cetyl, lauryl, capryl, tetrahydrofurfuryl alcohol, pentanol ormixtures of isomeric pentanols (which mixtures also may includen-pentanol), cyclohexanol, methylcyclohexanol, etc.; polyhydricalcohols, e.g., glycerol, pentaerylthritol, diphentaerythritol,mannitol, sorbitol, ethylene glycol, diethylene glycol, and others suchas are disclosed, for example, in Schaefer Patent No. 2,481,155;alcohol-ethers, e.g., ethylene glycol monomethyl ether, ethylene glycolmonoethyl ether, ethylene glycol monobutyl ether, diethylene glycolmonomethyl ether, diethylene glycol monoethyl ether, diethylene glycolmonobutyl ether, etc.; phenol and substituted phenols; and the like.

Illustrative examples of other modifying bodies that ca be incorporatedinto the fundamental reaction products, during their preparation orafter they have been formed, are melamine-aldehyde condensation products(e.g., melamine-formaldehyde condensation products), ureaaldehydecondensation products (e.g., urea-formaldehyde condensation products),urea-melamine-aldehyde condensation products (e.g.,urea-melamine-formaldehyde condensation products), protein-aldehydecondensation products, amiodiazine-aldehyde condensation products,aminotriazole-aldehyde condensation products, aniline-aldehydecondensation products, phenol-aldehyde condensation products (e.g.,phenol-formaldehyde condensation products), furfural condensationproducts, modified or unmodified, saturated or unsaturated polyhydricalcoholpolycarboxylic acid reaction products, ester gums, watersolublecellulose derivatives, natural gums and resins such as shellac, rosin,etc.; polyvinyl compounds such as polyvinyl alcohol, polyvinyl esters(e.g., polyvinyl acetate, polyvinyl butyrate, etc.), polyvinyl ethers,including polyvinyl acetals, e.g., polyvinyl formal, polyvinyl butyral,etc.

Coating compositions may be prepared from the thermosetting orpotentially thermosetting resinous compositions of this invention aloneor admixed with melamine-formaldehyde resins, fatty oil or fatty oilacidmodified alkyd resins, or other film-forming materials commonly usedin protective coating compositions. For example, a coating compositionmay be made containing, for instance, from 15 to 95 parts by weight of athermosetting or potentially thermosetting resin of the kind with whichthis invention is concerned and from 85 to parts of a fatty oil or fattyoil acid-modified alkyd resin, numerous examples of which are given, forexample, in Moore Patent No. 2,218,474, dated October 15, 1940.

Dyes, pigments, driers, curing agents (in some cases where a moreaccelerated cure is desired), plasticizers, mold lubricants, opacifiersand various fillers (e.g., wood flour, glass fibers, asbestos, mineralwool, mica dust, powdered quartz, titanium dioxide, zinc oxide, talc,China clay, carbon black, etc.) may be compounded by conventionalpractice with the synthetic materials of my invention, as desired or asconditions may require, in order to provide a coating, molding or othercomposition best adapted to meet a particular service use. Foradditional or more detailed information concerning the modifyingingredients that may be employed in producing coating compositions frommy resins, reference is made to the aforementioned Moore patent.

The modified and unmodified reaction products, more particularlyresinous reaction products, of this invention have a wide variety ofuses. For example, in addition to their use in the production of coatingcompositions, they may be employed as modifiers of. other compatiblenatural and synthetic resins. Thus, some of them advantageously may beused to improve the plasticity or fiow characteristics of thermosettingresins which have insutficient or unsatisfactory plasticity duringcuring to an insoluble, infusible state, e.g., certain urea-formaldehydeor melamineformaldehyde resins or molding compositions where better flowduring molding, without decreasing the cure time, is desirable. Thesoluble resins of this invention also can be dissolved in appropriatesolvents. Some of the solvents that may be employed to dissolve aparticular reaction product of my invention, in addition to others towhich reference hereinbefore has been made, include benzene, toluene,amyl acetate, butanol, methyl ethyl ketone, etc. The dissolved resinscan be used as laminatvarnishes in the production of laminated articleswherein sheet materials, e.g., paper, cloth, sheet asbestos, etc., arecoated or coated and impregnated with a resin solution, superimposed andthereafter united under heat and pressure. They also can be employed asan adhesive in making laminated plywood, laminated glass cloth, as animpregnant of pulp preforms from which molded articles thereafter aremade by subjecting the impregnated preforms to heat and pressure, asimpregnants for electrical coils and for other electrically insulatingapplications, for bonding together abrasive grains in the production ofresin-bonded abrasive articles such, for instance, as grindstones, sandpapers, etc., in the manufacture of electrical resistors, etc. They alsocan be used for treating textile materials (e.g., linen, rayon, andother cellulose-containing textiles, wool, silk, and other natural orsynthetic proteinaceous textiles, including nylon and textiles derivedfrom polyacrylonitrile and. acrylonitrile copolymers, and from casein,soyabeans, etc.), in filament, thread, yarn, fabric (woven or felted) orother forms, in order to improve the properties of such textilematerials, e.g., to increase the stiffness, to increase the servicelife, to impart shrinkage resistance thereto, or otherwise to enhancethe properties of the treated materials and to make them more useful orserviceable to the ultimate user. They also may be employed for treatingleather to improve its appearance and physical properties, and in thetreatment of paper or as a heater additive prior to the formation of thepaper.

I claim:

1. A composition comprising the product of reaction of ingredientscomprising (1.) a polymer of vinylene carbonate containing at least 10mole percent of combined vinylene carbonate and up to mole percent of adifferent compound which is copolymerizable with vinylene carbonate andwhich contains a CH C grouping, and (2) at least one nitrogenouscompound selected from the class consisting of ammonia, primary aminesand secondary amines, said reaction product being a carbamate.

2. A composition comprising the product of reaction of ingredientscomprising (1) a homopolymer of vinylene carbonate and (2) at least onenitrogenous compound seleeted from the class consisting of ammonia,primary amines and secondary amines, said reaction product being acarbamate.

3. A composition comprising the product of reaction of ingredientscomprising 1) a copolymer which is a product of polymerization of amixture of copolymerizable ingredients including (a) vinylene carbonateand (b) a different compound containing a CH =C grouping, the vinylenecarbonate of (a) constituting at least 50 mole percent of the saidmixture of copolymerizable ingredients, and (2) at least one nitrogenouscompound selected from the class consisting of ammonia, primary aminesand secondary amines, said reaction product being a carbamate.

4. A composition comprising the product of reaction of ingredientscomprising (1) an aldehyde and (2) a reaction product of ingredientscomprising (a) a polymer of vinylene carbonate containing at least molepercent of combined vinylene carbonate and up to 90 mole'percent of adifferent compound which is copolymerizable with vinylene carbonate andwhich contains a CHFC grouping, and (b) at least one nitrogenouscompound selected from the class consisting of ammonia, primary aminesand secondary amines, said reaction product being a carbamate.

5. A composition as in claim 4 wherein the aldehyde of (1) isformaldehyde.

6. A composition comprising the product of reaction of ingredientscomprising 1) formaldehyde and (2) a carbamate which is the reactionproduct of a homo polymer of vinylene carbonate with ammonia.

7. A composition comprising the product of reaction of ingredientscomprising (1) formaldehyde and (2) a carbamate which is the reactionproduct of a homopolymer of vinylene carbonate with a primary saturatedaliphatic amine.

8. A composition comprising the product of reaction of ingredientscomprising (1) formaldehyde and (2) a carbamate which is the reactionproduct of a homopolymer of vinylene carbonate with a secondarysaturated aliphatic amine.

9. A composition comprising the product of reaction of ingredientscomprising (1) formaldehyde and (2) a carbamate which is the reactionproduct of ingredients comprising (a) ammonia and (b) a copolymer whichis a product of polymerization of a mixture of copolymeriza-' bleingredients including (A) vinylene carbonate and (B) a differentcompound containing a CH C grouping, the vinylene carbonate of (A)constituting at least 50 mole percent of the said mixture ofcopolymerizable ingredients.

10. A composition comprising the product of reaction of ingredientscomprising (1) formaldehyde and (2) a oarbamate which is the reactionproduct of ingredients comprising (a) a primary saturated aliphaticamine and (b) a copolymer which is a product of polymerization of amixture of copolymerizable ingredients including (A) vinylene carbonateand (B) a different compound containing a CH =C grouping, the vinylenecarbonate of (A) constituting at least 50 mole percent of the saidmixture of copolymerizable ingredients.

11. 'A composition comprising the product of reaction of ingredientscomprising (1) formaldehyde and (2) a carbamate which is the reactionproduct of ingredients comprising (a) a secondary saturated aliphaticamine and (b) a copolymer which is a product of polymerization of amixture of copolymerizable ingredients including (A) vinylene carbonateand (B) a diflere'nt compound containing a CHFC grouping, the-vinylenecarbonate of (A) constituting at least 50 mole percent of the saidmixture of copolymerizable ingredients.

12. A liquid composition comprising (1) a soluble product of reaction ofingredients comprising (a) a polymer of vinylene carbonate containing atleast 10 mole percent of combined vinylene carbonate and up to molepercent of a different compound which is co polymerizable with vinylenecarbonate and which contains a CH =C grouping, and (b) at least onenitrogenous compound selected from the class consisting of ammonia,primary amines and secondary amines, and

I (2) a solvent for the reaction product of (1), which latter is acarbamate.

13. A heat-curable composition comprising a heatconvertible resinousproduct of reaction of'ingredients comprising (1) a polymer of vinylenecarbonate contain- I ing at least 10 mole percent of combined vinylenecarbonate and up to 90 mole percent of a different com pound which iscopolymerizable with vinylene carbonate 7 and which contains a CH =Cgrouping, and (2) at 7 grouping, and (2) at least one nitrogenouscompound selected from the clam consisting of ammonia, primary, 1

amines and secondary amines.

16. The method of preparing new synthetic composition which compriseseffecting reaction between in gredients comprising 1) an aldehyde and(2) a car bamate which is the reaction product of ingredients comprising(a) a polymer of vinylene carbonate containing at least 10 mole percentof combined vinylene carbonate and up to 90 mole percent of a differentcompound which is copolymerizable with vinylene carbonate and whichcontains a CH =C grouping, and (2) at least one nitrogenous compoundselected from the class consisting of ammonia, primary amines andsecondary amines.

17. A method as in claim 16 wherein the aldehyde of (1) is formaldehyde.

18. The process which consists essentially in reacting a homopolymer ofvinylene carbonate with aqueous ammonia at room temperature.

References Cited in the file of this patent UNITED STATES PATENTS OTHERREFERENCES Newman: J.A.C.S., vo1. 75, March 5, 1953, p. 1263 and 1264.

Gleim Sept. 27, 1949". i

UNITED STATES PATENT OFFICE v CERTIFICATE OF CORRECTION Patent No.2,930,779 March 29, 1960 Erhart K. Drechsel It "is hereby certified thaterror appears in the printed;

specification of the above numbered patent requiring correction and thatthe said Letters Patent should read as corrected below.

Column 3. line 30, for "compound" read compounds column 7, line .21, for,fiaryacrylic" read arylacrylic line 23, for 'fitaonic" read itaconicline 63, ior f'iodide," read halides t column 9, line 19-, for"herinafter" read hereinafter column 10, line 26' for "reductionoxidation" read reduction-oxidation line 32 after "total" strike out"of"; column 11, line 11, for "acryliate" read acrylate line 17, for"acylate read acrylate column 15, line 2, for "resinuo's' read resinousline 14 for "-pentaerylthritol," diphentaerythritol," readpentaerythritol, dipentaerythritol,

line 32, for r"amiodiazine" read aminodiazine-- Signed and sealed this.25th day of October 1960.

(SEAL) Attest:

KARL H. AXLINE ROBERT C. WATSON Attesting Officer Commissioner ofPatents I

1. A COMPOSITION COMPRISING THE PRODUCT OF REACTION OF INGREDIENTSCOMPRISING (1) A POLYMER OF VINYLENE CARBONATE CONTAINING AT LEAST 10MOLE PERCENT OF COMBINED VINYLENE CARBONATE AND UP TO 90 MOLE PERCENT OFA DIFFERENT COMPOUND WHICH IS COPOLYMERIZABLE WITH VINYLENE CARBONATEAND WHICH CONTAINS A CH2=C< GROUPING, AND (2) AT LEAST ONE NITROGENOUSCOMPOUND SELECTED FROM THE CLASS CONSISTING OF AMMONIA, PRIMARY AMINESAND SECONDARY AMINES, SAID REACTION PRODUCT BEING A CARBAMATE.